Desulfurization by hydrogen transfer reaction



United States Patent flice latented Mar. 8, 1955 ammo r BESUUWAWION WY; SEER Voorhies, In, Baton Rouge, La., assignoruosF'sso rand: ,meorporittion of Mona-wa ta ntarmy 122 i950 415,415

Thisv invention relatestoa novel process torremoving stilfurifrom sulfur-containing compounds itog'produce r'elafively sulturfrce jproducts' .by transfer of hydrogen from a hydrogen donor compound rWeran activated carbon catalyst under selective critical conditions.

-It has been discovered that sulfur-containing organic compounds, ..as svll as organic products having "taminants and impurities containing organically bound :sulfur, .may be freed of substantial amounts of such :sdlfur by contacting the sulfur-containing materials with tan activated carbon catalyst inthe ,presence .of a com- ;pound adapted for use was .a :hydrogen donor in -a ihytilrogen ttrans'fertreaction. .AmongthoseIhydrogendonors to be arrest ,practical :and luseftil :are the Cs naphih'enes, ,particulafly methylcyclohexane.

lti is rwcll -known the art that conventional catalytic hydrogenation :reactions can be employed to remove gstilfnr from organic compounds containing organically bound sulfur. I'IIhe problem of tremoving sulfur jfrom iiflh compounds or from mixtures containing r such corn- :pouu'ds Fistparticularly important in :eoniunction with the ipurifictition 'f'lhyiirocarbons :found inpetrdleum prod- :ucts, :eoal derivatives, shale oil, etc. Although .these sproducts have .ggenerally .been subjected -to Ihydrogenation ireactions, tactivated car-hon, the -catalyst .used in this ,process, is not a good catalytic hydrogenation catalyst .and would :not ordinarily 'tbe texpected to ifilIl'CllOIl as euch linnteact'ions -to :remove .sulfur. K

invention :further ilifers .from (conventional .hyduogenation reactions in shat-molecular hydrogen is :not supplied .to the .reaction .as'isuch, but is suppliedlin situ from athydrogen donor-such as .a 6 naphthene tor .an .isoparaffin. The invention :is especially applicable to catalyzed reactions in whichghydrogen is .directly transferredN- from,the hydrogen :donor ,to the sulfur jbe'ing removed 'from'the organic molecule. In general, the :sultur :removed from the organic compounds is @subsequently converted by -;the Lhydrogen transfer reaction .to arsulfide, ms'ually -hy drogen .suliide. Generally, the hy- -drog'en transfepreactioniis carried out in .the vaponphase f-the use \of a :solid activated carbon catalyst, 131- *though under certain instances, .rliguid acidic catalysts may also be used. Thetusemf =thetselective activated carbon catalyst results in much greater selectivities in the removal of sulfurtogive-the-ilesired sulfur-free prod- "B013 and a substantial treduetion ;=in mndesirable' degradation ireactions'of the starting materials to gaseous prodoots and carbonaceous bjy products.

N8phth6fl9afl :bede'fined-tas saturated-compounded the .generalformula flzflmhaving closed @links composed of metliylene groups. The tnaphthenic thydrocarbons whieh 'can the employed :as hydrogen donors :are' tprefteralily :those having rsix acyclic carbon atoms, that is, eyelchexanerandtits derivatives. :Naphtlrenic rings #hav- :ingifour: orfilessmarbon atoms are:too unstabledofunction satisfactorily. fllltylatcd :derivativestof tthese xnaphthenes michvasrmethyleyctohexane'ean 3180 tbeemployed. tDur ing the courseof tthe reaction, tthe'inaphthenes iare' alehydrogenated "to produce aromatic type products. For

instance, when 'cyclohexane is used, it is converted to benzene and-when*methylcyclohexane is vused, 'it .is convenedto toluene. The hydrogen atoms which are thus removed from the 'naphtnenes are catalytically utilized in tliepres'ence or the activated carbon catalyst to comwith "the sulfur present as organically bound sulfur in the feed "stock, thereby removing the sulfur from "the reed stock and converting it into an easily separable *t'orm. Cyclohexane and its higher homologues are particularly adapted f'for use in 'the'role of hydrogen donors because the removal of six hydrogen atoms from cycloheitane zconverts itto the completely aromatized benzene.

The reaction'is carried out in vapor ,phase in the presence of the activated carbon catalyst and under condit'ions of temperature, pressure, feed rates, andltheilike, .ISI) chosen as to produce the maximum possible removal of sulfur ffrom the ,feed stock and at the same time to obtain high selectivity and relatively pure final sulfur- ;fre'epro'ducts. T he equipment employed for this process may be of .any type known .to those skilled in the .art for efiecting a vaporphase catalytic reaction. Thus, for example,. liquid feed is charged toa vaporizer from which zth'e'irestilting'ffeed vapor'spass through a preheating zone and thence 'into the catalytic reaction zone in which the vapors are contacted with the solid carbon catalyst. The teilluen't vapors from the reaction .zone :are .subseguently cooled and condensed to produce a liquid reaction ,product and non-condensible .gases.

'fIZhe selectivity which is achieved by this process vcannot readily -be obtained by any vother hydrogenation method. For example, catalytic hydrogenation tusing "free'hy'drogen extraneouslyintroduced in conjunction with a hydrogenation catalyst :is not at all selectiveand uses .getterallya catalyst such as nickel ..or supported nickel, ".both .of which are .much less rugged and durable.

'ltlis of especial advantage 'in theme of .thishydrogen transfer :process that using .an activated carbon, there .is 'a of side reactions. For instance, under optimum conditions, substantially no cracking .or gas folmatiou takes place to give breakdown or decomposition productsof the naphthenic compound. There is .also -.a minimum of polymerization of the reactants and the treactiomproducts to give'hig'her molecular weight condensed materials and tarry by-products.

.Ihe tcatalyst which has been found -to be especially tuse'iiil-iintcarnying tout .the reaction to remove organically iboun'cl sulfur is activated .carbon, :a particularly sensitive catalyst which :gives .a minimum amount of degradative cracking reactions to produce gaseous by-products ,and coke. Ellie activated :carbon is derived from a variety of sources, ,including lignite, petroleum, coke, bituminous teoah or'selected pure organic compounds. The catalyst should have a very ,high surface area and a relatively low content nof volatile material. The amount of suriface area is -.considered to .be directly related to catalytic activity. highlyssuitable carbon-catalyst for thisconrVE'ISlOILiS one of coal origin rwhichthas averyhigh-suraface .areatof =the 'order-of 1,000 to 11,100 squarezme'ters per tof catalyst. When the catalyst is in use and istbeing slowly deactivated, it is believed that the'surface area actually decreased because the'pores of the carhan catalyst slowly become filled with organic deposits. ln-rorder tto ;;reactivate .the catalyst, these deposits :must be zremoved from -the pores of the catalyst. This 51'6- tmOVm isiaccomplishedby a reactivationiprocedure. For :instance, tthe 2 activated carbon :catalyst :is regenerated by stripping with. a gas such :as steam, nitrogen, flue gases, tetc eat elevated 'temperatures, e., 1350-'1600 F. A

" spreferred method for regeneration ofthe carbon catalyst some extent, todirectly burn the organic deposits from by fractionation,

' best from the viewpoint of operational donor, as well as any hydrogenated product present as the result of the use of unsaturates in the reaction. Any hydrogen sulfide present in the liquid may be removed by extraction, caustic washing, or by other conventional methods for'removal of hydrogen'sulfide. Unchanged or incompletely desulfurizedreactants can be recycled, together with fresh sulfur-containing feed The liquid reaction product'so'obtained in any suitable manner, for example,

and fresh hydrogen donor material. If desired, an inert I diluent such as, for example, a portion of the noncondensible gaseous products can be employed. It is also possible to recycle a part of the product as a diluent.

Although there is no necessity for a diluent in order to v obtain the desired features of th'e'reaction, the use of some such inert material may at times be desirable to effect more etficient and simpler control of the reaction.

It will be understood that the exact conditions cinployed in carrying out the desulfurization-reaction will. be determined by the nature of the feed constituents, the

desired removal of sulfur per pass, and'the exact catalyst being employed. The reaction may be carried out under pressures ranging from atmospheric to superatmospheric with the restriction that the reaction must be carried out in the vapor phase. The range of pressures However, it is advantage that may vary from 1 to 100 atmospheres.

atmospheric pressures be employed.

In general, the range of temperatures for carrying out the desulfurization reaction will be of' the order of 600-1100 F. Optimum temperatures for the reaction are considered to be 750 950 F. At temperatures below this range, the rate of reaction tends to fall off and become somewhat slow and the removal of sulfur is substantially incomplete, even after adequate contact with the catalyst. At temperatures higher than this limit, there is noticed an increased tendency towards the occurrence of side reactions such as thermal cracking, gas formation, polymerrzatlon, and other undesirable reactions. The total feed rates employed will generally lie in the range of 0.3 to 5 liquid volumes per volume of catalyst per hour. It is considered that'the contact time may be relatively short, such as 0.1 to 1 second, to

- achieve optimum selectivity and satisfactory removal of sulfur.

When desulfurization of thiophene was studied-in the presence of methylcyclohexane, using-an activated carbon catalyst at atmospheric pressure, it was discovered that the catalyst temperature has a profoundeffect'on the percentage of reduction in sulfur obtained in the liquid product. It was demonstrated that at-temperatures around 750 F., only about 38% of the sulfur was removed. If temperatures of about 950 F. wereemployed, about 93% of the total sulfur in the-feed was removed during the desulfurization. Temperatures intermediate between these two extremes gave the expected intermediate results. In each case, theweight of sulfur present in the feed being studied was a constant value and no extraneous hydrogen acceptor was added during the reaction. as the hydrogen donor in a hydrogen transfer reaction to remove sulfur from diethyl sulfide in the presence of 2-butene as a hydrogen acceptor and at catalyst temperatures of around 950975 F., it was found that the feed stock was removed. Under similar conditions,

using thiophene as the feed stock in place of diethyl sul- When methylcyclohexane was employed Results reported were obtained after a 'and bring it to the desired temperature.

fide, from 40% to 50% of the sulfur was removed. Where n-heptane, a saturated 'parafiin not capable of functioning as a hydrogenj donor, was employed in place of methylcyclohexane in an attempted desulfurization of thiophene at about 950KB, relatively poor results were obtained. These resultsindicated that only about oft e-su u p sen w ifimQWd it presence or absence of Z-butene as a hydrogen acceptor did 1not appear to cause appreciable difference in the resuts.

s .The amount of methylcyclohexane-fed.to..the hydrogen transfer reaction shown in proportion to..the .sulfur compound fed, is best adjusted such that a substantial excess'of the hydrogen donor is present-in relation to the amount of sulfur compound to be desulfurized. In typical reactions, from 0.27 to 0.63 mole of sulfur compound were contacted'with from 1'.75'to 3.51 moles of methylcyclohexane over an activated carbon catalyst to effect desulfurization. In other words, reaction mixtures ave'been used to which enough 'naphthene has been added to provide about 2.8 to 13 'moles'of naphthene per mole of sulfur-containing compound present; Where" a compound such as Z-butene'is'added' tofunction asa hydrogen acceptor, experiments -indicate from 3.64 to 4.99 moles of 2-butene in relation to the proportions of other reactants indicated above to be adequate;

As to the types of sulfur-containing feed stocks which ylated thiophenes, and other thiophene derivatives, 'diethyl sulfide, diethyl disulfide, dipropyl sulfide, dibutyl sulfide, diamyl sulfide, mercaptans, various types of -sulfur acids, etc.- The process is especially useful for desulfurizing petroleum fractions, as for instance, naphtha fractions containing organically bound sulfur which must be removed before the fractions can 'beused for many purposes. In general, compounds must bensed whose desulfurized products are sufficiently stable to withstand the relatively high temperatures and-yet emerge from the reaction zone as intact molecules. Furthermore, the process can be applied to sulfur-containing feed materials, such as are often found in refinery streams,

while processes such as catalytic hydrogenation cannot be applied since the presence of even small amounts of sulfur in conventional catalytic hydrogenation rapidly inactivates the sulfur-sensitive'catalysts and renders them wholly inoperative and useless. The process may be executed in a batch, intermediate, or continuous manner. Generally, better conversions are obtained with multi-pass processes. The catalyst may be employed .in'a fixed bed, moving bed, or in a fluidized manner, depending on the type of operation desired.

This invention will be better understood with reference to the following examples and tables indicating the results obtained in the desulfurization reaction of thiophene and diethyl sulfide in the presence of a hydrogen donor and, in some cases, hydrogen acceptor-compounds.

single pass operation unless otherwise specified.

EXAMPLE I The hydrogen transfer experiments were-carried out in ageneral way by passing the liquid feed comprising the appropriate mole ratio of-methylcyclohexane and 2- butene together with the sulfur-containing compound, through a vaporizer and preheater to vaporize the feed The heated feed vapor was contacted with the activated carbon catalyst' bed at the temperaturesand feed rate conditions specified by the data of the table. The resulting products were condensed and analyzed as to distribution of '-constituents and for the residual sulfur content 'of the feed. In Table I shown below, the'sulfur-containing feed compounds were diethyl sulfide and thiophene:

Table Methyleyclo- Methyle'y'e l'o "n-heptane.

exane. g hexane. hexane. meth l Sulfide--. 1; mo henelghiophenemh TRANSFER REAo'noNs Myth-liquid feed rate 0.6 v./v./hr.]

Metnymyclo- 1 Moles MethylcyelqhexaneFed.

5M2; leqb'zle e. f 1 Avg. Catalyst Temp., Product Analysis: W

LCarbon we rercentnutput.

Gas Wt. Percent Qutput 04 Product, (hferden't 4 ole: PercentrSelcJ-tb gereentbutput.

n e-m. (instead or memyicyusneian :From Table I above,- it isevidentthat hydr'og'entransfer desulfurizatio'n is 'hi'g'h with a imethyloyclohe "butene ffee'd mixture in the presence for'g' containing compounds such "as dietliyl -s"1'ilfide phene. ':The data of theabove table show of thiophene in methyl cyclohexane the liquidtproduct contained 2.4% sulfur as compared to 5.07% sulfur for the feed. This corresponds to a 53% reduction in sulfur content of the oil. When n-heptane was employed as a hydrogen donor in the place of methylcyclohexah oil product contained 4.0% sulfur as compared'to" in the feed. This corresponds to a. 28.3% rednctionn'n sulfur content. It is shown that for the conversiono'f thiophene sulfur a naphthene rather than a 's'ti'a ht chained parafiinic hydrocarbon is a preferred hydrogen donor. 1

EXAMPLE II v p 1 Table ll DnSULFu-RIZATION BYHY Run? ""6 Temp., F 751 800 797 348 Feed Steam,,Wt.-Percen ,25- .25 None None GMbbl'lQ'WCiPQTO v "2 6 :05- 3H 1.8 Oa- Gas, Wt. Pere'e 0. 9 2. 4 1. 0 3. 2 e.+.o11 we 96.5 97.6 425.6 $5.0 'I-OILS Wt. Percent ofFe 96.4 $7.? 95. 3 $193. 0 gn e.50 0.41 0.30 "0.23 e 39 54.5 65 AII G y.. 50.2 52.0 52.6 52.1 B remlne N0 5 5, 5 5; 8 1 lstillaltlon, ASJM- V .53.; P1, initial 1? 212 200 185 v 5% 242 239 214 256 -24! 254" 5:55 212 :264 284 272 297 "284 311 -296 329 312 336 99 360 Final 414 kPereent Reeovery 98 ;P ereent Residue- '1- 0 Percent Loss 1. 0

.Aitter causticwashmg. lt w'ill be noted from a-compari'son 'li'sted abovedn Table III, that'th'e presence of results-"inn decreased jtliiopheneeenve'rs'wn. is

as-' 'also 'bee'n noted with other fee'd stock's. lnereasin t e temperature resulted in inereased eenversion. Tdble eawmmsrmrmicmm [Feed rate: 01 5'vl/vi/hr4' 200 cci'aet."O catalystfatmospherlepressdrei 2 hr. run' lengthJ Feed 'Gonditlons Liquid Product Type Percent llernp, ,Mol. -bbl. -=1?ereent- Percent -S -S "F. Percent. of Feed 8 -'ofFeed j 1 Thio'pheneinMetliyleyelohekane 942 None. 1,045 84.' 2 93.2 do {852 None "163 88:0 "81.3 5305 None 1135' 8657 14. 1 153; None- 132 90.0 .38. 1 95 1 None, 937 63. 3 '22. 8

EXAMPLE III Data havebeen obtained which :show'that thiophene sulfur can be removed by a hydrogen transfer reaction 80 .centthiophene. V v H thiophene was x'substanfziallyj: refnoved by' h-ydrogen transfr 'reactions.

' -llllp'resents data showing that "the "'750,*F. operation which gave very little 'dem'llfurization resulted m anoil Jfpr'oduc't that contained-fbtter than-10% d 11'i ng n1uchhigher'than the feed. "Asthe-temp "increased; the amount of high boilingfiilatfia (166!8 d 200 p s.

Table IV EFFECT OF PRESSURE EFeed: Heavy virgin naphtha plus 1 volume percent thipohcnc (0.06

weight percent 8). Conditions: 0.5 v./v./hr.; 25 weight percent steam; 200 cc. act. catalyst; 2 hr. run length; pressure and temperature as indicated] Coke Wt. pcr- Percent Run Pressure, Temp" Wt. C3 g cent S Reducp. 8. i. g. F. Per- Percent in oil tion in cent product Sulfur Although the use of pressure to lower the temperature of reaction may be of only slight benefit fornaphtha feed stocks, for less refractory feeds the advantages of lowering the reaction temperature would be more pronounced since, operating in this way, excessive cracking might be avoided.

.All of the runs reported in Tables III and IV were made using a feed rate of 0.5 v./v./hr. Further data indicate that increasing the feed rate results in lowering the thiophene conversion, but tends to give an increase in' selectivity. This is shown by the data in Table V obtained using a feed of 10 volume per cent thiophene in methylcyclohexane.

Table V 2. A process for reacting a naphthene containin at I least 6 carbon atoms per molecule with thiophene, w ch comprises forming a mixture of the naphthene with the thiophene, in which mixture a sufficient amount of the naphthene is present to supply at least two hydrogen atoms for each atom of sulfur in the thiophene, and contacting the resulting naphthene and thiophene mixture in vapor phase with a catalyst consisting of activated carbon at 650 to 950 F. at a rate corresponding to about 0.3 to 5 liquid volumes of mixture per volume of catalyst per hour, whereby the naphthene is dehydrogenated to an aromatic hydrocarbon in transferring hydrogen therefrom directly to sulfur of the thiophene.

3. A process as defined in claim 2, in which the naphthene is principally methyl cyclohexane.

4. A process for reacting a naphthene containing at least 6 carbon atoms with a dialkyl sulfide containing at least 0.23 weight percent sulfur to convert the naphthene into an aromatic hydrocarbon by direct hydrogen transfer reaction with the dialkyl sulfide, which comprises mixing the naphthene with the dialkyl sulfide to provide a mixture containing about 2.8 to 13 moles of naphthene per mole of dialkyl sulfide, passing the resulting mixture of the naphthene and dialkyl sulfide in vapor phase into contact with a catalyst consisting of activated carbon at .650 to 950 F., and contacting said mixture with the catalyst at. a rate corresponding to 0.3 to 5 liquid volumes of mixture per volume of catalyst per hour to convert the naphthene into an aromatic hydrocarbon by transfer of hydrogen from the naphthene directly to the sulfur of the dialkyl sulfide.

EFFECT OF FEED RATE ON DEBULFURIZATION BY HYDROGEN TRANSFER [Feed: 10 vol. percent thiophene in methylcyclohexane (4.79% S).

atmospheric pressure; 200 cc. act. 0 cats] Operating conditions: yst; run length adjusted to 200 cc. total fee Products, Wt. Percent Percent R 5:22 Material Percent Reducun v /v [hr Balance 04+ Product in Coke Oa-Gas liquid Sulfur 1a 0. 5 88 I 1. 21 74 14 "0. 5 98. 3 7. 7 0. 8 91. 5 *2. 26 53 15 1 99. 2 0 O. 4 99. 6 1. 99 58 16 2 99. 1 0. 0 0. 3 99. 7 2. 48

After caustic washing. "Used 25 wt. percent feed steam. A

50 5. A process according to claim 4 in which the naph- Increasing the feed rate appears to have given an increased selectivity for desulfurization. Since increasing the temperature gives greater desulfurization, it appears that operation at a high feed rate that is somewhat greater than 0.5 v./v./hr., and at a high temperature (850900 F.) would result in a high sulfur reduction with good selectivity for naphtha feed stocks. Broadly, temperatures of 650-950 F., with atmospheric and superatmospheric pressures and feed rates to produce maximum desulfurization and selectivity within these temperature and pressure ranges, can be satisfactorily employed in this particular type of hydrogen transfer-desulfurization reactions.

What is claimed is:

1. In a process for effecting removal of sulfur from an organic compound containing at least 0.23 weight percent of combined sulfur by a direct transfer of hydrogen from a naphthenic hydrocarbon of at least 6 carbon atoms per molecule, the steps which comprise admixing the sulfur-containing organic compound with a sufiicient amount of the naphthenic hydrocarbon to provide about 2.8 to 13 moles of naphthene per mole of sulfurcontaining compound in the resulting mixture, passing the mixture into contact with a catalyst consisting of activated carbon at a temperature in the range of 650 F. to 950 F. at a rate of about 0.3 to 5 liquid volumes oflmixture per volume of catalyst per hour, whereby ,the naphthenic hydrocarbon is dehydrogenated to a corresponding aromatic hydrocarbon and sulfur of the sulfur- 'containingorganic compound is converted to hydrogen sulfide, carrying out said reaction with a minimum content.

theme is methyl cyclohcxane and the dialkyl sulfide is diethyl sulfide.

6. A process for simultaneously aromatizing naphthenes and effecting desulfurization of a petroleum naphtha fraction containing at least 0.23 weight percent of organically bound sulfur but having a relatively small naphthene content, which comprises admixing a sufficient amount of naphthenic hydrocarbons with said petroleum naphtha fraction to provide about 2.8 to 13 moles of naphthenes per mole of sulfur compound, passing vapors of the petroleum naphtha fraction enriched in naphthenes into contact with a catalyst consisting of activated carbon at a temperature of 650 F. to 950 F. at a rate corresponding to 0.3 to 5 liquid volumes of mixture per volume of catalyst per hour to transfer hydrogen directly from the naphthenes to the sulfur of sulfur-containing impurities in the petroleum naphtha fraction, and recovering a resulting mixture of aromatic hydrocarbons and petroleum naphtha hydrocarbons freed of the sulfur-containing organic impurities.

7. A process according to claim 6 in which the mixture of hydrocarbons and sulfur-containing impurities are passed into contact with the activated carbon catalyst at a feed rate greater than 0.5 volumes per volume of the activated carbon per hour.

References Cited in the file of this patent UNITED STATES PATENTS 1,884,495 Zurcher Oct. 25, 1932 1,913,941 Mittasch et al. June 13, 1933 2,411,726 Holroyd et al Nov. 26, 1946 2,573,726 Porter et a1 'Nov. 6, 1951 2,606,141 Meyer Aug. 5, 1952 2,626,286 Voorhies et al. 'Jan. 20, 1953 

1. IN A PROCESS FOR EFFECTING REMOVAL FO SULFUR FROM AN ORGANIC COMPOUND CONTAINING AT LEAST 0.23 WEIGHT PERCENT OF COMBINED SULFUR BY A DIRECT TRANSFER OF HYDROGEN FROM A NAPHTHENIC HYDROCARBON OF AT LEAST 6 CARBON ATOMS PER MOLECULE, THE STEPS WHICH COMPRISE ADMIXING THE SULFUR-CONTAINING ORGANIC COMPOUND WITH A SUFFICIENT AMOUNT OF THE NAPHTHENIC HYDROCARBON TO PROVIDE ABOUT 2.8 TO 133 MOLES OF NAPHTHENE PER MOLE OF SULFURCONTAINING COMPOUND IN THE RESULTING MIXTURE, PASSING THE MIXTURE INTO CONTACT WITH A CATALYST CONSISTING OF ACTIVATED CARBON AT A TEMPERATURE IN THE RANGE OF 650* F. TO 950* F. AT A RATE OF ABOUT 0.3 TO 5 LIQUID VOLUMES OF MIXTURE PER VOLUME OF CATALYST PER HOUR, WHEREBY THE NAPHTHENIC HYDROCARBON IS DEHYDROGENATED TO A CORRESPONDING AROMATIC HYDROCARBON AND SULFUR OF THE SULFURCONTAINING ORGANIC COMPOUND IS CONVERTED TO HYDROGEN SULFIDE, CARRYING OUT SAID REACTION WITH A MINIMUM AMOUNT OF DEGRADATION OF THE HYDROCARBONS TO GASEOUS AND CARBONACEOUS BYPRODUCTS, AND RECOVERING THE RESULTING AROMATIC HYDROCARBON PRODUCT OF LOW ORGANIC-SULFUR CONTENT. 